Novel cycloalkenecarboxanilides



United States Patent C) 3,352,992 NOVEL CYCLOALKENECARBOXANILIDESHerbert Schwartz, Smaragdplein 186, Uh'echt, Netherlands N Drawing.Filed May 27, 1965, Ser. No. 459,418 Claims. (Cl. 260-557) ABSTRACT OFTHE DISCLOSURE Novel cycloalkenecarboxanilides of the formula XIIwherein R is a cycloalkene radical having 3 to 8 carbon atoms and X isat least one member selected from the group consisting of halogen andlower alkyl, lower alkoxy and halogenated lower alkyl of 1 to 7 carbonatoms and n is an integer from O to 3. The invention also relates tonovel post-emergence herbicidal compositions and to a novel method ofcontrolling Weeds.

XII

wherein R is a cycloalkene radical having 3 to 8 carbon atoms and X isat least one member selected from the group consisting of halogen andlower alkyl, lower alkoxy and halogenated lower alkyl of 1 to 7 carbonatoms and n is an integer irom 0 to 3. The halogen substituent can befluorine, chlorine, bromine or iodine, preferably chlorine or bromine.The compositions preferably also contain a surfactant or emulsifier.

Th cycloalkenecarboxanilides of Formula I are excellent post-emergenceherbicides and may be used in the form of dusting preparations,solutions, emulsions or dispersions.

In order to prepare a solution suitable for direct spraying, there maybe used, for example, a mineral oil fraction of high or medium boilingrange, such as diesel oil or kerosene, or coal tar oils, or vegetable oranimal oils and also hydrocarbons such as alkylated naphthalenes, ortetrahydronaphthalene, if desired, with the use of xylene mixtures,cyclohexanols, ketones, or chlorinated hydrocarbons, such astetrachlorethane, trichlorethylene or trior tetrachlorobenzenes.

Aqueous preparation suitable for application can be prepared by theaddition of water to emulsion concentrates, pastes or wettable powders.As emulsifying or dispersing agents there may be used non-ionicproducts, for example, condensation products of ethyleneoxide withaliphatic alcohols, amines or carboxylic acids containing a hydrocarbonradical having about 10 to 30 carbon atoms, such as a condensationproduct of octadecyl alcohol with 25 to 30 molecular proportions ofethylene oxide, or of soya bean fatty acid with 30 molecular proportionsof ethylene oxide or of commercial oleylamine with 15 molecularproportions of ethylene oxide or of dodecylmercaptan with 12 molecularproportions of ethylene oxide. Among anion active emulsifying agentsthere may be mentioned the sodium salt of dodecyl a1- cohol sulfuricacid ester, the sodium salt of dodecylbenzene sulfonic acid, thepotassium or triethanolamine salt of oleic acid or abietic acid or of amixture of these acids, or the sodium salt of petroleum-sulfonic acid.As cation-active dispersing agents there may be used quaternary ammoniumcompounds, such as cetyl-pyridinium bromide or di-(hydroxyethyl)-benzyl-dodecyl-ammonium chloride.

For making dusting or scattering preparations there may be used as solidcarriers talcum, kaolin bentonite, calcium carbonate or calciumphosphate or carbon, cork meal or wood meal or other materials ofvegetable origin. The various preparations can be rendered more suitablefor the various Ways in which they are to be used by the known additionof substances which improve the dispersing, adhesiveness, resistance torain or penetration capacity of the compositions. As such substancesthere may be mentioned fatty acids, resins, glue casein or, for example,alginates or the like.

The cycloalkenecarboxanilide compositions can also contain herbicidaloxidizing ions to obtain synergistic herbicidal compositions. Examplesof suitable oxidizing ions are dipyridylium salts such as1,1'-ethylene-2,2-dipyridylium dibromide (Diquat),1,1'-dimethyl-4,4'-dipyridylium di(methylsulfate) (Paraquat), etc.;alkali metal and alkaline earth metal nitrate salts such as sodiumnitrate, calcium nitrate, etc.; herbicidal arsenical compounds such asmonoalkanearsonic acids and lower dialkanearsinic acids such asmethanearsouic acid, propanearsonic acid, dibutane-arsinic acid,dipropanearsinic acid, cacodylic acid (hydroXy-dimethylarsine oxide),etc., and their alkali metal, alkaline earth metal and amine salts sucha monosodiurn methanearsonate (MSMA), disodium methanearsonate (DSMA),calcium hydrogen methanearsonate, and amine salts of the said arsonicacid where the amine is ethanolamine, di-ethanolamine, triethanolamine,isopropylamine, triisopropanolamine, mixtures of alkylamines having 8 to14 carbon atoms, etc.

The method of the invention for killing weeds comprises contacting theweeds with a toxic amount of at least one cycloalkenecarboxnilide of theformula 3 wherein R is a cycloalkene radical having 3 to 8 carbon atomsand X is at least one member selected trom the group consisting ofhalogen and lower alkyl, lower alkoxy and halogenated lower alkyl of 1to 7 carbon atoms and n is an integer from to 3.

The compositions, when applied to fields as aqueous solutions suitablefor direct spraying, may be applied by the broadcast method or row orband method at a dosage level of about 0.5 to pounds per acre or higher.The dosage level for the row method is usually about onequarter of thedosage level of the broadcast method.

In the following examples there are described several preferredembodiments to illustrate the invention. However, it should beunderstood that the invention is not in- 4 EXAMPLE II Generalpost-emergence herbicidal activity To demonstrate the general herbicidalactivity of the cycloalkenecarboxanilides of the invention, the saidcompounds were applied to seven dilferent type of plants according tothe following procedure:

The compounds were prepared as 10% emulsion concentrates in two specifictypes of solvent systems a follows.

tended to be limited to the specific embodiments. Formula F:

EXAMPLE I Percent by wt. H Compound 10 The cycloa kenecarboxamhdesreported in Table were Triton X461 10 prepared by reacting thecycloalkenecarboxylre aCld ha- Solvent F 80 lide with the correspondinganiline compound.

TABLE I Formula 50M: 0 1 1k b mud M w nt itrog n Compound 10 6 s meTriton X-161 10 Galcu- Found Solvent 50M 80 lated 3-ch1oro-1-c e10entenecarboxanilide..- 123424 6.32 6. 43 3'-brom -1- y r n en rb nn;121-123 5 27 Triton X-161 1s a blend of anionic and non-lomc alkyl4;-clfllqmawclopentenewboxamhde--- 159461 aryl polyether alcohols andorganic sulfonates. Solvent F 3 ,4 -(]Jchloro-1-cycl0penteneca1'box- 3Oanilide 122-123 5,47 5,66 1s a 50:50 by volume mlxture of drethyleneglycol mono- 3-chloro4-methyl-1-cyclopentenecarboxamnde 114,115 5.95 15butyl ether acetate and Yelsicol ARSO (methylated naphSfchloro-l-cyclohexenecarboxanilide 39- thalenes). Solvent 50M 1s a20:80 by volume mixture of 3 g i i igg f 5 19 5 ethyl acetate andVelsicol ARSO. Before application the 3-ch1oro:4 n 1ti1 lyElJHeZrneconcentrates were diluted to a concentration of 2000carboxam'lide 139-140 5. 61 5. 82 3-chloro-3-eyclohexenecarboxanilide188-89 5.95 6.01 of the compound bemg tested j3,4-dichloro-3-cyclohexenecarbox- The seven crops to be tested had beenplanted in flats anilide 137-138 5.19 5. 46 3, cmom4, methy1 3cyclohexene 10 to 12 days before the tests and were well estabhshedcarboxam'lide 125-126 5. s1 5. 92 seedling. The plants were sprayed onan endless belt spray 3-trifluoromethyl'1-cyclopentene- 106F108 M9 M0 yt pe at a belt p d f 4 wk: per h ur 3-t7rifluoromtithyl-l-cyclohexene- 2WhlCh applied to each flat containing the seven crops the carboxanili e118-120 5.20 5.3 v 3mmuommethyl a eyclohexene spray solution at anequivalent of 25 gallons per acre. carboxanilide 84-86 5. 20 5. 37 Theplants were then kept under constant daily SllIVell- 5linrlgggfn-imgghoxy-l-cyclopentena n IOHH 5. 57 5' 65 lance tor a periodof 7 to 14 days. The final phytotoxicity -ch1oro-2'methoxy-1cyclohexenedata was recorded at the end of 14 days and theplants 1g g ggggifi g%fibig lg' ibigfiI"' were scored for phytotoxicityratings on a scale from 0 carboxanilide 81-83 5.28 5.29 (no injury toplants) to 10 (all the plants were killed).

The results of the tests are summarized in Table II.

TABLE II Phytotoxicity Rating Cycloalkenecarboxanilide Solvent BeetsTomatoes Radish Johnson Oats Wheat Cucumber Grass3-ohloro-1-cyclopentenecarboxanilide Fl 9 6 6 7 3 2 4 1' a a v v v 4 a1- 1 1: c b "nil'de F 51 81 71 9 6 2 3 3 bromoeye open one ar OXa 1 50M31 7i 2- 1 STE 0 1 4-ehloro-1-cyc1opentenecarboxanilide F 51 41M v 51 81 6 1 50M 51M 71M 71M 2 0 0 2 3,4-dichloro-1-cyclopenetenecarboxanilideF 10 1O 10 8 6 3 10 50M 9 9.5 9.5 2 4 7 73-chloro-4-methyl-l-oyclopentenecarb oxanilide F 10 10 7 9 2 0 1 50M 5 99 0 0 0 5 3,4-dichloro-1-cyclohexenecarboxanilide F 10 6 7 3 1 5 6 50M 88 8 2 1 6 5 3-chloro-4-methyl-1-cyclohexenecarb oxanilide F 9 9 6 8 2 06 50M 6 7 2 2 0 0 4 3-chloro-3-cyclohexenecarhoxanilide... F 10 9 10 3 13 5 50M 10 10 10 2 4 2 9 3,4-dichloro-3-cyclohexenecarboxanilide. F 10 29 3 1 p 1 6 M 10 10 9 4 4 3 10 3-chloro-4-methyl-3-cyclohex enecarboxanilide. F 9 7 9 6 2 1 5 50M 9 9 10 2 0 0 s ControL 0 0 0 0 0 0 0iIn11ibited. TBlip burn. MMorphogenic change.

5 EXAMPLE n1 Selective post-emergence herbicidal activity 6 The tableshows the clear-cut herbicidal selectivity of said compounds on Johnsongrass with a minimum of injury to cotton.

Various modifications of the compositions of the inven- 5 tion may bemade without departing from the spirit or cycloaklenecarboXfmlhdes wereall tested as 1 scope thereof and it is to be understood that theinvention 611151121211 cloncfentratles uimg f 223; fig i s g is to 1belimited only as defined in the appended claims. an I11. 0 asovenCOIlSlSlDgO 0 0 gaijn; Butyl Carbitol Acetate and TlitOll X-161 whichWES A cycloalkenecarboxanilide of the formula diluted with 100 ml. ofwater. The said solution was used X 0 u for spraying the plants at adosage of 0.8 pound of the II cycloalkenecarboxanilide per acre. NH C RThe flats sprayed contained plants sown in rows alternating cottonplants with Johnson grass and at the 2 i g g i i g g igg time ofspraying, the cotton was in the seedling state and a oms an 1s a eas Hemem r 6 cc m the Johnson rass was about 1/ to 1 i ch h i ht or groupconsisting of halogen and lower alkyl, lower alkoxy the Seedling SgtagePots of Conan g p ig in and halogenateg lower ally] of 1 to 7 carbonatoms and nis an inte er romlto WhlCh the cotton was 1n the 4-leaf stagewith 2 well de- 3' chlro l cyclopeutenecarboxanflma veloped true leavesand 2 cotyledonary leaves. Pots of red 3r bromo 1cyclopentenecarb0Xanflide kidney beans having 2 well-developed trueleaves and 4 3' 4' di h1 1- l t b flid P of 5111311, medium and largeJohnson grass and P 5. 4'-chloro-1-cyclopentenecarboxanilide. oftomatoes were also sprayed. The data is presented in 6, 3'- h1-4'-methyl-1-cyclopenteneearboxanilide Table III using the phytotoxicityratio of O to 10. 7. 3'-ch1oro-1-cyclohexenecarboxanilide.

TABLE III Phytotoxicity Rating Cycloalkenecarboxanilides Flats PotsJohns Grass .Tcglnson Cotton Cotton Beans Tomatoes on mss Small MediumLarge 3-ch1oro1-cyc1opentenecarboxanilide 10 4 0 2 0 4 2 93-bromo-1-cyclop entenecarb oxam'lida 9. 5 3 0 4 2 10 94-chloro-l-cyclopenteneearboxanilide 8 2 0 3 1 10 93,4-dich1oro1-eyc1opentenecarboxanilid 1 8 2 1. 5 4 4 8 6 73'-chloro4-methyl-l'cyclopentenecarboxanilide- 8 3 1 5 3 10 53-cl1loro-1-cycloh exenecarboxanilide 7 3 1 2 4 8 7 53'-ch1oro-4-methyl-1-cyelohexenecarb oxanilide- 8 2 1 1 3 10 6 83-chloro-3-cyc1ohexeneearboxanilide 4 1 2 3 4 6 7 83,4-dichlor03-cyclohexenecarboxanilide. 3 4 2 4 7 1 4 6 Control 0 0 0 00 0 0 0 EXAMPLE IV 8. 3, '-dich1oro-1-cyc1ohexenecarboxanilide.

Selective post-emergence herbicidal activity Using the procedure ofExample HI, pots of seedling cotton, cotton in the 4-leaf stage,seedling Johnson grass and Johnson grass about 5 cm. high were sprayedwith 9. 3'-chloro-4-methyl-1-cyclohexenecarboxanilide. 10.3'-trifluoromethyl-l-cyclopentenecarboxanilide. 11.3-trifluoromethyl-l-cyclohexenecarboxanilide. 12.3-trifiuoromethyl-3-cyclohexenecarboxanilide. 13.3-chloro-3-cyclohexenecarboxanilide.

'-triflnoromethylcycloalkenes and the phytotoxicity rat- 14.3,4'-dich1oro3-cyc1ohexenecarboxanilide. ings were made. The results aresummarized in Table IV. 15.3-chloro-4-methyl-3-cyclohexenecarboxani1ide.

TAB LE IV Phytotoxicity Rating Compound Seedling -Leaf Seedling 5 cm.

Cotton Cotton J. Grass J. Grass3-trifluoromethyl-l-eyelopenteneearboxanilide 2 1 73-trifluoromethyl-l-cyclohexenecarboxanilide- 3 1. 5 8 103'-trifluoromethyl-3-eyclohexenecarboxanjlide 1 1 9 References CitedHawkins et al.: J. Chem. Soc. (1955), pp. 14628. Tifieneau et aL: Compt.Rend., vol. 212, .pp. 581-5

